The Free Energy Function of the Doi-Edwards Theory: Analysis of the Instabilities in Stress Relaxation

The molecular model used by Doi and Edwards in developing their rheological theory admits a simple form for the free energy of deformation, at least when the independent alignment approximation is used. A general expression is derived, as well as the specific form which applies to an instantaneous shear deformation. The latter is used to analyze the possibility that instabilities, or “deformational phase separations,” arise in the course of stress relaxation experiments. The results of the analysis are compared with recent experimental results by Osaki and Kurata and by Vrentas and Graessley which show an anomalous relaxation behavior.